Catalytic hydrocarbon conversion process



Jan. 22, 1946., W. E. Ross ETAL CTALYTIC HYDROCARBON CONVERSION PROCESS Filed March 1,- 1944 Nom A ar E .n T u.. nu

Patented Jan. 22,"19446 CATALYTIC HYDROCARBON CONVERSION PROCESS William E. Ross, Berkeley, and George J. Carlson,A El Cerrito, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application March 1, 1944, Serial No. 524,820 .1o calms. (c1. 26o-'sassi This invention relates to the execution of catalytic reactions and/or treatments with the aid metal halide of the -Friedel-Crafts type and relates more particularly to the execution of hydrocarbon conversions and treatments wherein hye minum.

' Catalysts and contact materials comprising metal halides of the Friedel-Crafts type are nding ever-increasing application in processes directed to the practical execution of many widely varying types of catalytic reactions andl treatments. Of these catalysts and contact materials those comprising a halide of aluminum, for example, .aluminum chloride, aluminum bromide, etc., are of particular practical importance in the treatment or conversion of hydrocarbons or hydrocarbon-containing materials. Catalytic hydrocarbon conversion processes in which they are applied to advantage comprise, among others, those involving isomerization,-alkylatlon, polymerization and condensation reactions. The nature of the particular catalyst or contact material comprising the aluminum halide and the manner in which it is employed will vary with the particular process. Although in certain proc-- esses it is used in a solid form and in other processes may be used in either a solid or iluid form, in a great number of processes, particularly among those of recent development, it is often highly advantageous and sometimes essential that the catalyst used be of a fluid type. Available fluid type catalysts orV contact materials vary considerably from one another. The iiuid type catalyst may comprise the aluminum halide as a suspension or aV solution in a suitableA liquid vehicle. The liquid vehicle may comprise a hydrocarbon or hydrocarbon mixture which may be a part or all of the materials treated. Other carrying liquids may comprise a hydrogen halide such as HC1; alkyl halides; SO2; or any other liquids inert at the operating conditions.

Another type of fluid aluminum halide-containing catalyst comprises the aluminum halide as a solution or suspension in a suitable molten salt or mixture of molten salts. 'I'he molten salts may simply function as the carrying medium or they may act as a catalyst modifier or as a separate catalyst component to form a true mixed molten salt catalyst. Suitable salts which may be combined with the aluminum halide to provide a fluid molten salt type catalyst comprise, for example, Aa halide of one or more of catalysts or contact materials comprising a of the following: As, Zr, Nb, Mo, Pd, Sn, Sb, Hf, Ta, W, Tl, Pb, Bl, U, Zn and the alkali and alka- `line earth metals. Particularly suitable molten salt type aluminum halide-containing catalysts comprise -a molten mixture of aluminum halide and a halide of antimony, for example, a melt comprising AlClz dissolved in SbCla; a molten mixture of aluminum halide and at least one halide salt of an alkali or alkaline earth metal.

Still another type of uid aluminum halidecontaining catalysts comprises a iiuid organoalumlnum halide complex. The uid complex catalysts may be prepared by mixing an aluminum halide, for example, aluminum chloride and/or aluminum bromide, with an organic compound under suitable conditions resulting in the interaction of the aluminum halide with the organic compound and/or decomposition products thereof. Suitable organic compounds with which the aluminum halide may be combined under conditions resulting in the obtaining of a desired organo-aluminum halide complex comprise, for example, aromatic hydrocarbons, such as benzene, toluene; hydrocarbon fractions, such as an aromatic kerosene extract; cyclic oleiins, such as cyclohexene, cyclopentene and alkyl-derivatives thereof; parafnic and olefinic hydrocarbons of temperatures, for example, not substantially in` excess of about C., generally inthe presence of an added hydrogen halide for a sumcient length of time to result in the formation of a liquid or sludge consisting essentially of only an organo-aluminum halide complex.

1t is to be pointed out, however, that the invention is in no wise limited to the use of a particular type of catalyst comprising a metal halide of the Friedel-Crafts type, nor by the method of its preparation.

In carrying out the process with the aid of these catalysts the catalyst and hydrocarbon, or hydrocarbon mixture, to be converted or treated are passed countercurrently, generally in the presence of an added hydrogen halide, through a reaction zone maintained under operating conditions defined by the particular reaction to be favored. In other methods of operation the re actants are bubbled through, or otherwise subjected to intimate contact, with a catalyst mass in arating zone and at least a portion of the thus separated catalyst recycled to the reaction zone.

At least partly spent catalyst or catalyst residue, consisting predominantly of a sludgy organo-aluminum halide complex is generally drawn from the system at one or several points thereof which may comprise the reaction zone,v

catalyst separating zone and fractionating system. This results in the continuous production and accumulation of a considerable amount of aluminum halide-containing, at least partly spent, catalyst or catalyst residue. In such processes eflcient operation on a practical scale generally precludes the utilization of the catalyst until all of the aluminum halide has-been cornpletely expended and continuous or intermittent regeneration, and/or readjustment of catalyst, must generally be relied upon to maintain the catalyst activity at a practical level. This involvesl the further substantially continuous separation and production of considerable amounts of relatively inactive aluminum halidecontaining sludge. In certain types of operations wherein catalysts consisting essentially of molten salt mixtures comprising the aluminum halide are used, the presence of even relatively small proportions of sludge considerably reduces the activity of the catalyst and continuous sludge removal must then be resorted to to maintain the catalyst at a sufciently high level of catalyst activity to assure elcient operation of the process. This again results in a considerable accumulation of at least partly spent catalyst containing considerable proportions of catalyst components. Feasibility of practical operation of a process employing these catalysts is generally dependent upon the recovery, to at least a substantial degree, o f the aluminum halide 'content of the thus continuously accumulated inactive sludgeor at least partly spent catalyst. Methods available heretofore have been not only cumbersome and costly but seldom enable substantially complete recovery of the active catalyst component from 'the discarded at least partially spent catalyst or catalyst residue, thereby detracting considerably from the efciency of the operation.

Separation of the uncombined aluminum halide from the sludge may be eiected to at least a substantial degree by scrubbing with a suitable solvent rsuch as, for example, a paramnic hydrocarbon in which free catalyst components, such as aluminum halides, possess appreciable solubility but in which the sludge, consisting essentially of organo-aluminum halide complexes, is generally relatively insoluble. The greater proportion of the aluminum halide in the sludge is, however, lin the form of the organo-metal halide complex from which it cannot be freed by mere solvent treatment. Attempts to destructively distill the residue by methods resorted to heretofore are not only cumbersome but present acute difficulties in recovery of substantially all of the aluminum halide and particularly in its return into the system.

It is an object of the present invention to provide an improved process for the more efficient execution of catalytic reactions with the aid of metal halides of the Friedel-Crafts type. wherein the metal halide is eiliciently and continuously recovered within the system.

Another object of the invention is the provision of animproved process for the more efficient execution of hydrocarbon conversions with the aid of catalysts comprising an aluminum halide, wherein the aluminum halide is eillciently and continuously recovered within the system.

Another object of the invention is the provision 'of a process for the more efllcient execution of catalytic hydrocarbon conversions with the aid of uid catalysts comprising a mixture of molten salts comprising a metal of the Friedel- Crafts type, wherein catalyst components are efficiently and continuously recovered with the system.

Another object of the invention is the provision of an improved process for the more eflicient conversion of hydrocarbons with the aid of iluid catalyst melts comprising .a halide of aluminum, wherein catalyst components areeiiciently and continuously recovered within the system.

A further object of the invention is the provision of an improved process for the morel eilicient recovery of the metal halide constituents from fluid mixtures comprising metal halides of the Friedel-Crafts type.

A still further object of the invention is the provision of an improved process for the more eincient recovery of the aluminum halide content from at least partly spent aluminum chloridecontaining catalysts and catalyst residues obtained in the treatment of hydrocarbons with the aid of aluminum halide-containing catalysts. Other objects and advantages of the invention will become apparent from the following detailed description thereof.

' In accordance with the invention, continuous recovery within the system of the metal halide component from at least partly spent catalysts or catalyst residues which are produced within a process 'wherein hydrocarbons are contacted with a catalyst comprising a metal halide of the Friedel-Crafts type, is obtained by the passage of the at least partly spent catalyst or. catalyst residue, substantially as rapidly as formed, into a distillation zone. Within the distillation zone the spent catalyst is subjected to a temperature suillciently high to effect the formation of a vaporous product comprising the metal halide. l

' the system, catalyst residue formed within the system, a hydrocarbon or hydrocarbon fraction,

'through the catalyst recovery and reaction zones. Such inert liquids may comprise, in the case of hydrocarbon conversions, molten salts, halogenated hydrocarbons, paraffin hydrocarbons or paralnic hydrocarbon fractions diiering in boiling range from the material being treated, SO2, CS2, etc.

In a preferred embodiment of the invention the at least partly spent catalyst or catalyst residue is subjected to a solvent treatment or extraction within the system prior to the distillation operation. Suitable solvents in processes treating or converting hydrocarbons comprise a hydrocarbon or hydrocarbon fraction available within the system, for example, a portion of the feed. By the scrubbing, at least a substantial part or the free metal halide constituent of the at least partly spent catalyst or catalyst residue is removed therefrom prior to passage of the latter to the distillation zone.

in order to set forth more fully the nature oi' the invention without, however, intending to limit the scope of the catalytic treatments or couver sions to which it may be applied, it will be described in detail herein in its application to the isomerization of hydrocarbons with reference to the attached drawing, wherein the single figure shows a more or lessy diagrammatical elevational View of one form of apparatus suitable for the execution oi' the invention. y

an isomerizable saturated hydrocarbon such as, for example, butane from any suitable source, is forced by means of pump i through valved line t into an intermediate part oran extraction zone. The extraction zone may consist of a column t provided with suitable packing material, baiiies or the like. Within column the butane is contacted in the liquid phase with avportion oi at least partly spent catalyst emanating at least in part i'rom the reaction aone as described more fully below. Liquid butane comprising extracted catalyst components is passed from column t through valved line it and heat exchanger d into a reaction zone. The reaction zone may consist oi a suitable reactor it provided with stirring means l and a separating chamber il. Within reactor t the butane is contacted with a suitable isomerization. catalyst comprising a metal halide oi the Friedel-Crafts type and preferably a fluid type catalystcomprising a halide or aluminum. A particularly efllcient isomerization catalyst comprises, for example, a molten mixture oi antimony halide and an aluminum halide. A molten mixture of aluminum chloride and a molten mixture of AlCl: and SbCh containing from about 3 to about 24 mol percent of aluminum chloride is highly suitable. It is to be understood, however, that the invention is in no wise limited to a specific catalyst of the molten salt type and other catalyst melts may be employed including, forexample, any of the following molten mixtures: aluminum chloride-sodium chloride potassium chloride, aluminum chloride-sodium chloridezinc'chloride, aluminum chloride-sulfur dioxidezinc chloride, aluminum chloride-sodium chloride-potassium chloride-zinc chloride,V etc. A part or al1 of the halide components of the cataiyst may comprise halides other than the chlorides, for example, the bromides.

The temperature to be maintained within reaction chamber 6 may vary inaccordance with the particular hydrocarbon treated and catalyst used. In the isomerization of saturated hydrocarbons temperatures of, for example, from about 50? C. to about 300 C., and preferably from about 80 C. to about 200 C., are satisfactory. 'I'he l temperature within reaction chamber 8 is controlled by judicious heat input or withdrawal from the butane stream by means of heat exchanger 5 and, if needed, by additional heating means not show n in the drawing. The isomerization reaction is preferably executed in the presence of ahydrogen halide such as, for example, hydrogen chloride. The hydrogen chloride is introduced into the charge l:owing through line d by means of line I0. `Under these conditions butane will be converted to isobutane Within reactor t.

The isomerization reaction may be executed in the vapor or liquid phase. When operating in the liquid phase a pressure at least suiciently high is maintained within reactor t to complete at least a substantial part oi the butane in the liquid phase.

Within separating chamber d a lsubstantial de gree of separation between catalyst melt and hy., drocarbon will be edected. The supernatant hydrocarb'on layer, which ingeneral will comprise some admixed or dissolved catalyst, is withdrawn from separator d and passed through line d into a vaporizing zone. The vaporizing zone may suitably consist oi the lower part of a column EZ, an intermediate part of which is provided with suitable packing means, baes or the like.. With.. in column it separation of hydrocarbons from entrained catalystl components is eected with the aid of heating coil it. Since antimony chloe ride is relatively volatile, its separation from, the hydrocarbon within column it. isy aided by the introduction of cold hydrocarbon reflux into the upper part of the column by'means oi valved line it. Vapore, comprising isobutane, unconverted normal butane and hydrogen chloride promoter. are passed from the upper part or column it through line it and cooler iii into an' acc later it. In passing through cooler i "i the stream is cooled to a temperature suiidciently low to ei lect the condensation of butanes.

From accumulator id liquid comprising isobutane and normal butane is forced by means ci pump tu through line 2i into a stripping "uw ai. Uncondensed gases and vapors may be sepa rateiy withdrawn from accumulator it through valved line it and passed in part or in their entirety by means not shown in the drawing to column 22. Within stripping column 22 the hydrogen chloride promoter is separated from the hydrocarbon material and removed therefrom through valved line 25. A portion or all oi' the hydrogen halide promoter passing through line 25 is recycled through Vvalved'line it to line d.

Make-up hydrogen chloride is introduced into line lll from an outside source by means of valved line 20. A liquid fraction comprising normal butane and isobutane is passed through valved line 21 into a fractionator 28. Within fractionator 28 a liquid fraction comprising normal butane is separated from a vapor fraction comprising iso,- butane. The liquid fraction is withdrawn from column 28 through valved line 29 and forced in part or in its entirety through valved line 30 to sludge in even relatively smallamounts' has aI decided detrimental effect upon the catalyst melt as a whole. Maintenance of a high level of catalyst activity is attained by the substantially continuous elimination of the sludge or spentlcatalyst from the system -by continuously passing at least a portion of the catalyst phase separated in catalyst separator 8 through valved lines 35 and 36 into the upper part of column 3. The por tion of at least partly spent catalyst thus introduced into column- 3 will pass countercurrently to the upward flowing butane charge. In its passage through column 3 active, free catalyst components comprising antimonychloride and aluminum chloride are dissolved in the butane stream and passed therewith to reactor 6. The remaining portion of the at least partly spent catalyst comprising components which are at least partly spent with respect to their ability to catalyze the isomerization reaction remains insoluble in the butane stream and is separated as a heavier fluid catalyst residue. The fluid catalyst residue will generally consist predominantly of aluminum chloride-hydrocarbon complexes. The hydrocarbon charge to the system is preferably preheated, for example, with the aid of a suitable heat exchanger 3'l to a temperature favorable to the extraction operation. 'I'his temperature will vary with the nature of the material being treated and the particular catalyst used. In the treatment of paraillnic hydrocarbons temperatures in the approximate range of from about 50 C. to about 125 C. and preferablyfrom about 50 C. to about 100 C. are found suitable. The pressure within column 3 is always sufficiently high to maintain at least a substantial portion of the hydrocarbon stream passing therethrough in the liquid phase.

It has been found that the fluid catalyst residue separated within extractor 3 will comprise any hydrocarbon-aluminum chloride complexes formed within reactor 6. It has also been found that this material is substantially insoluble in the hydrocarbon feed which contributed to its formation and will not undergo decomposition or disintegration to any substantial degree in the extraction zone, whereas the still active antimony chloride-aluminum chloride catalyst possesses an appreciable degree of solubility in the normal butane. The composition of the fluid catalyst residue separated within column 3 will vary to some degree with the nature of the material treated and operating conditions used.

The elciency with which the separation of active free catalyst components are separated from the spent catalyst comprising aluminum chloride-hydrocarbon complexes in scrubbing column 3 is exemplified byl the following example:

Example I -`i` Partly spent catalyst obtained in the isomerization of butane with a fluid catalyst melt consisting of A1Cl3 dissolved in SbCls, drawn from the catalyst separator (separator 8) of the syshydrocarbon-aluminum chloride complexes, and which nad the following composition: f

'I'he fluid catalyst residue separated in column 3, as is apparent from the foregoing example. contains a considerable proportion of valuable alutem was found to have the following composition:

Weight per cent AlCla 7.3 SbCl3 88.3 FeCh 0.7 Carbon 2.0 Excess Cla-- 1.3

,into a. distillation zone.

minum chloride. The rate at which'catalyst is withdrawn from separating chamber 8 and passed to the upper part of extractor 3 may vary within the scope of the invention. As pointed out, however, it is highly advantageous to effect the catalyst Withdrawal at a rate sulciently great to prevent the accumulation to any substantial degree of even partially spent catalyst within the reactor. The amount of catalyst residue thus accumulated in operation of the plant at a high level of catalyst activity will therefore generally be sufficiently great to seriously detract from efflcient operation of the process unless the aluminum chloride be recovered therefrom. Recovery must not only be high but continuous to enable the maintenance of optimum catalyst composition in the system without recourse to excessive amounts cf make-up aluminum chloride from an outside source.

In accordance with the invention continuous and highly eilicient catalyst recovery is effected within the system by forcing the catalyst residue from column 3 through valved lines 39 and 40 The distillation zone may comprise a still 4| positioned in a furnace structure I2. It has been found that by the judicious application of heat the catalyst residue charged to the still is converted to a vaporous product comprising hydrocarbons, sublimed aluminum chloride and a carbonaceous residue. Heating of the catalyst residue at a. temperature of, for example, from about 200 C. to about 500 C., and preferably from about 350 C. to about 400 C. has been found suitable. A Worm or screw 43, or similar device, is provided to move the coky residue within the still to outlet 44 whence it is eliminated from the system. Under these conditions at least a substantial part of the aluminum chloride is recovered in the vaporous products. 'Ihe hydrocarbons comprised in these products are found to consist predominantly of light parailinic compounds, free of any intermediate hydrocarbons of a nature capable of interfering with efficient recovery of the aluminum chloride.

The catalyst residue removed from scrubber 3 will generally possess sufficient fluidity even at ordinary temperatures to permit its passage without diiliculty to the distillation zone. If desired, however, a portion of the butane feed to the system may be diverted from line 2 and forced through valved lines 46 and 4l into line 40 to further dilute the sludge flowing therethrough.

The excellent recovery of high purity aluminum chloride from the catalyst residue is evidenced by the following. Catalyst residues, taken from the bottom of scrubbing column 3 during a yseries of large scale butane isomerization operation with a uid catalyst melt, consisting of AlCla dissolved in SbCh, under conditions substantially as described, and having the composition indicated in Table A were subjected to disvalved line tot.

tillation temperatures. The amount of aluminum chloride recovered in the vaporous product, coky residue obtained, and maximum still temperatures employed are indicated in Table B.

Table A yAnal sis weight per cent of catalyst resiy due charged to still- 1 2 3 4 O (l 62 62 29 29 2. 1 2. 1 Excess chloride 5. 2 5. 2

Table E Recovery l 2 3 4 Weight per cent of A1015 in total charge.. 75. 3 74. 3 63 72 HC1 es weight per cent of total charge.... 6. 6 6. 8 Colry residue weight percent of total c arge 26. 7 22. 7 39' 36 Maximum still temperature, DC 400 405 400 Vapore comprising sublimed aluminum chloride and hydrocarbons are passed from still il 'through conduit @it into a catalyst recovery zone. The catalyst recovery zone may comprise a suitable enlarged chamber or tower it optionally provided with suitable baiiies or the like. Within catalyst recovery tower dit the vapors are brought into contact with a downwardly flowing stream or a suitable liquid medium, for example, a molten salt such as antimony trichloride which is introduced into the upper part of the column through lin a preferred method of exeouting the process of the invention at least a part of the liquid fraction'separated in column it and consisting predominantly of antimonytrichloride is passed from the lower part thereof through valved lines tt and .56 into the upper part of column de. In its downward passage through column 49 the aluminum chloride emahating from still di is dissolved in the antimony 'trichloride stream and the resulting antimony line 56 passing from line 52 directly into line` 54 is provided for the passage of a part or all of the antimony trichloride fraction from column i 2 directly to reactor 6.

Although antimony trichloride because of its low melting point and the appreciable solubility of aluminum chloride therein is particularly advantageous as a liquid suitable for recovering the sublimed aluminum chloride, it is to be pointed out that the process of the invention is in no wise limited to the use of a particular molten salt and other molten salts or mixtures thereof, possessing sufiiciently low melting point and no adverse effect upon catalyst or reactants under execution of the process, may suitably be used. The invention is, furthermore, not limited to the use of molten salts as the medium forl conveying the recovered aluminum chloridel and any suitable liquid, inert or possessing no disadvantageous effect upon reactants or catalyst under the conditions of operation, may be used.

If desired, a part or all of the liquid medium introduced into the catalyst recovery tower di! may comprise a part of the iiuid catalyst. This may be Withdrawn from any suitable point in the reaction zone and passed directly to the top of column de. The catalyst is, however, preferably taken from the catalyst layer, separated out in catalyst separator t by judicious manipulation of valves 5l and 5t. A portion oi the catalyst layer from catalyst separator t is thus passed through lines t5, t2 and til into the upper part of column du, while another portion of the catalyst layer is passed through lines t5 and 3b to the top of scrubbing column t. 'If desired, a part or all or the liquid introduced into the upper part of column @it may comprise a part of the hydrocarbon charge to the system. Such portion of the hydrocarbon charge is diverted from'line 2 and passed through lines de, 52 and 5d into the upper rt of the catalyst recovery column, or may be diverted from line d, through valved line iid. When a hydrocarbon or a hydrocarbon mixture other than the hydrocarbon charge is used as the carrying liquid for the recovered aluminum chloride,

these are separated from the reaction products by any suitable means comprising, for example, fractionation, eirtractive distillation, solvent enL1 traction or any other step not shown in the drawing. When a hydrocarbon or hydrocarbon mixture higher boiling than the hydrocarbons being treated or converted is used as the liquid introduced into the column 39, this is recovered from the reaction effluent together with entralned antimony trichloride as bottoms in column it and the resulting mixture, or a portion thereof, returned to the catalyst recovery tower.

Vapors, comprising hydrocarbons, vinert gas and hydrogen chloride not condensed in col d@ are eliminated overhead therefrom through valved line di. The following is the analysis of the acid-free gas evolved during the distillationv of the catalyst residue number 4 `oi" the above Table A Gas analysis: y mol percent Hydrogen 5.7

` C1 to Cs saturated hydrocarbons 66.2 Ethylene 0.4 Propyiene 0.0 Butylenes 0.2 Butanes 22.4

Higher boiling. than butane.' 5.1

The evolved gas is substantially paramnic and contains a considerable proportion of butane which, together with the recovered hydrogen chloride, is preferably recycled to the conversion zone thereby further utilizing material heretofore eliminated in the catalyst residue. Vapors and gases leaving column 49 through valved line 5i are forced in part or in their entirety through line 6 l leading into line I6. If desired, the overhead from column 49 may b'e passed by means not shown in the drawing from line 5| to charge line 2. The latter has the advantage of eliminating any olen content of the gas by contact with at of these points, is passed into the upper part of column I9 substantially as described above. At times it may be desirable, particularly when utilizing fluid catalysts of the organo-metal halide complex type to pass spent or partly spent catalyst separated from the reaction products directly into still 4I. To this effect a valved line 62 is provided enabling the passage of a portion of the catalyst layer from separator 8 into still 4 I.

The invention thus enables the more eiiicient execution of catalytic conversions with the aid of catalysts comprising metal halides of the Friedel-Crafts type under conditions providing for the substantially continuous elimination of spent catalyst from the system substantially as rapidly as formed, with simultaneous continuous and substantially complete recovery of the metal halide content of the spent catalyst and its continuous return into the system, thereby enabling maintenance of a high level of catalyst activity over far greater periods of operation with a minimum requirement of make-up catalyst'from an outside source.

We claim as our invention:

l. En a catalytic hydrocarbon conversion process wherein hydrocarbons are converted b`y contact with a fluid catalyst melt comprising antimony trichlorlde and aluminum chloride at conversion -conditions in a conversion zone. and a liquid fraction comprising entrained antimony trichloride is separated from reaction products, the steps which comprise withdrawing a portion of at least partlv spent catalyst from said conversion zone. scrubbinfr said portion of catalyst with the hydrocarbons to be converted in a scrubbing zone. therebv separating catalyst components by solution from a iluid catalyst residue consisting essentially of aluminum chloridehydroca rbon complexes. passing hydrocarbons comprising dissolved catalyst'components from the scrubbing zone to the conversion zone. passing said fluid catalyst residue from said scrubbing zone into a distillation zone. maintaining a temperature sumciently high in said distillation zone to convert said catalyst residue into vapors comprising aluminum chloride and a coky residue, contacting said vapors with said liquid fraction comprising entrained antimony trichloride separated from reaction products thereby dissolving aluminum chloride in saidliquid fraction. and passing the resulting liquid comprising antimony trichloride and dissolved aluminum chloride to said conversion zone.

2. In a catalytic hydrocarbon conversion process wherein hydrocarbons are converted by contact with a iluid catalyst melt comprising a halide of antimony and a halide of aluminum at conversion conditions in a conversion zone, and a liquid fraction comprising entrained antimony halide is separated from reaction products, the steps which comprise withdrawing a portion of at least partly spent catalyst from said conversion zone, scrubbing said portion of catalyst with aluminum halide-hydrocarbon complexes the scrubbing zone, passing hydrocarbons comprisving dissolved catalyst components from the scrubbing zone to the conversion zone, passing said uid catalyst residue from said scrubbing zone into a distillation zone, maintaining a temperature suillciently high in said distillation zone to convert said catalyst residue into vapors comprising aluminum halide and a coky residue, contacting said vapors with at least a portion oi said liquid fraction comprising entrained antimony halide separated from the reaction products thereby condensing aluminum halide, and passing the resulting liquid comprising antimony halide and condensed aluminum halide to said conversion zone.

3. In a catalytic hydrocarbon conversion process wherein hydrocarbons are converted by contact with a iluid catalyst comprising a halide oi' aluminum at conversion conditions in a conversion zone, eilluence from the conversion zone is'y passed into a vaporizing zone, and a liquid fraction comprising entrained catalyst is separated from hydrocarbon reaction products in said vaporizing zone, the steps which comprise withdrawing al portion of at least partly spent catalyst from said conversion zone, scrubbing said portion of at least partly spent catalyst withdrawn from the conversion zone with the hydrocarbons to be converted in a scrubbing zone, thereby separating active catalyst components by solution from a uid aluminum halide-containing catalyst residue in said scrubbing zone, passing hydrocarbons to be converted comprising dissolved catalyst components from the scrubbing zone to the conversion zone, passing said iluid catalystresidue fromv the scrubbing zone into a distillation zone, maintaining a temperature sufciently high in said distillation zone to convert 40 said catalyst residue into vapor comprising aluminum halide and a coky residue, passing said liquid fraction from said vaporizing zone into contact with said vapors comprising aluminum halide in said distillation zone, thereby condensing aluminum halide and passing the resulting liquid comprising condensed'aluminum halide from said distillation zone to said conversionzone.

4. In a catalytic hydrocarbon conversion process wherein hydrocarbons are converted by contact witha iluid catalyst comprising a metal hadide of the Friedel-Crafts type at conversion conditions in a conversion zone, efiiuence from the conversion zone is passed into a vaporizing zone, and a liquid fraction comprising entrained catalyst is separated from hydrocarbon reaction products in said vaporizing zone'r the steps which comprise withdrawing a portion of at least partly spent catalyst from said conversion zone, scrubbing said portion of at least partly spent catalyst withdrawn from the conversion zone with the hydrocarbons `to be converted in a scrubbing zone, thereby separating active catalyst components by solution from a fluid metal halide-containing catalyst residue in said scrubbing zone, passing hydrocarbons to be converted comprising dissolved catalyst components the hydrocarbons to be converted in a scrubbing v zone, thereby separating catalyst components comprising antimony halide by solution from a iluid catalyst residue consisting essentially of` from the scrubbing zone tr the' conversion zone, passing said iluid catalyst residue from the scrubbing zone in to a distillation zone, maintaining a temperature sufllciently high in said distillation zone to convert said catalyst residue into vapors comprising metal halide and a coky residue, passing said liquid fraction from said vaporizing zone in 'to contact with said vapors comasoatoo prism metal halide in said distinction me. thereby condensing metal halide, and passing the resulting liquid comprising condensed .metal halide from said distillation zone to said conversion zone.

5. In a catalytic hydrocarbon conversion process wherein hydrocarbons are converted by concatalyst components by solution from a fluid catalyst residue consisting essentiallyof aluminum chloride-hydrocarbon complexes in said scrubbing zone, passing hydrocarbons comprising dissolved catalyst components from the scrubbing to the conversion zone, passing said fluid catalyst residue from said scrubbing zone into a distillationl zone, maintaining a temperature suftact'with a iluid catalyst melt comprising alntiv 7 catalyst from said--conversion zone, passing said portion of partly spent catalyst withdrawn from the conversion zone into a distillation zone,

'maintaining a temperature suiilciently high in said distillation zone to convert said portion of at least partly spent catalyst into vapors comprising aluminum halide and a coky residue. contacting said vapors with aiiuid melt comprising antimony halide, thereby dissolving aluxnium halide 'in said melt, and passing the resulting fluid melt comprising dissolved aluminum halide to said conversion zone. f

8. In a process of treating at least partly spent duid catalysts comprising hydrocarbon-alumiciently high in said distillation zone to convert said catalyst residue into vapors comprising aluminum chloride and a coky residue, contacting said vapors with molten antimony trichloride thereby dissolving aluminum chloride -in said antimony trichloride, and passing the resulting molten antimony trichloride comprising dissolved aluminum chloride to said conversion zone. f 8. In a catalytic hydrocarbon conversion process wherein hydrocarbons are converted by contact with a fluid catalyst melt compri'singfantimony trichloride and aluminum chloride at conversion conditions in a conversion zone, the steps which comprise' withdrawing a portion of at least partly spent catalyst' from said conversion zone. scrubbing said portion of catalyst withdrawn from the conversion zone with the hydrocarbons to be converted thereby separating catalyst comride from the distillation zone to said conversion o v complexes, subjecting said catalyst residue toav .sumciently elevated temperature to produce a 7. In a catalytic hydrocarbon conversion process wherein hydrocarbons are convertecljiy contact with a .iluidcatalystv melt comprising a halide of aluminum and a halide oi' antimony at conversion conditions in a'oconversion zone, and reactor emuence is passed into a product separating'zone, the steps which comprise separately withdrwin a portion of at least partly spent num halide complexes and uncombined catalyst components comprising aluminum halide, the steps which comprisescrubbing said catalyst with a paramnic hydrocarbon solvent, thereby separating catalyst components comprising aluminum halide by solution from a fluid catalyst residue comprising aluminum halide-hydrocarbon complexes, subjecting said catalyst residue to a sumciently elevated temperature to produce a vapor comprising aluminum halide and a coky residue, and contacting said vapor with amelt comprising a halide of antimony. thereby dissolving said aluminumhalide-in said melt.

9. In a. process or treating at least partly spent uid catalysts comprising hydrocarbon-aluminum halide vcomplexes and uncombined catalyst rating catalyst components comprising aluminum halide by solution from a duid catalyst residue comprising aluminum halide-hydrocarbon vapor comprising aluminum halide and a ook? residue, and contacting said vapor with the -parafiinic hydrocarbon sol ent comprising dissolved catalyst componen obtained in said scrubbing operation thereby condensing alumif-` metal halide by solutionv from a iluid residue comprising hydrocarbon-metal halide complexes. subjecting saidreaidue to -a sumciently elevated ltemperature to produce a vapor comprising said metal halide and a coky residue, and contacting said vapor with the parafiinic hydrocarbon solvent comprising dissolved catalyst components obtained in said scrubbing operation, thereby condensing said metal halidevapors. .WILLIAM E. ROSS.

' GEORGE J. -CARLSCN3 

